Wrinkle coating



` .F9-b. 1, 1933. F. B. ROOT 1,996,594

WRINKLE COATING Filed March "7, 1929 FgLE.

FRANK BRIAN 300212,01' EAST Patented Feb. 7, 1933 UNITED vvSTATI-:sPATENT OFFICE ORANGE, enmarcar. company, or NEW WRINKLE Application ledMarch 7,

This invention relates to varnishes and enamels and methods of utilizingsuch compositions and particularly to compositions of this characterwhich' result in the production of the so-called wrinkled finishes, aswell as to articles carrying such finishes.

.In U. S, Patent N o. 1,639,892 to Frank B. Root, granted October 30,1928, there was disclosed for the first time in the art the productionof wrinkling finishes and compositions to be used therefor together withprocesses of producing Qsuch finishes on articles of manufacture. Thispatent represents a wide departure from the prior art. In that priorart, considering the production of continuous surface' finishes,attempts were always made to attain a substantially smooth surface and.irregularities of surface finish were avoided, the efforts beingdirected to the production'of smooth finishes.' The production ofwrinkle finishes, satisfactorlly controlled so that the desired effectscould be produced, was-taught to the art for the first time in thatpatent.

-For the purposes outlined in that patent,

it is set forth that drying oils are an essential v. characteristic ofthe wrinkling finish varmshes and compositions. Among the dryin oilsmentioned in that patent'and suggeste or these purposes are linseed oil,perilla oil, and China-wood oil, particularly preoxidized China-woodoil, the blown product being emphasized as giving a very desirableeffect.

As explained in that patent, when the surface is coated with a varnishof the desired composition and exposed to drying conditionsadvantageouslyi at an elevated temperature, a wrinkle-finish\of pleasingand attractive appearance results. The wrinkling seems to be due torapid oxidation of the surface of the applied film forming a skin overthe less oxidized material on the interior of the' film, the surfaceskin increasing in volume and expanding laterally and the less oxidizedmaterial on the interiorv of the film y being of lower viscosity,flowing into the fold produced by expansion of, the surface skin.

The general effect is that of the level surface carrying ridgesprojecting therefrom and running more or less irregularly over the `isthe production of treated drying oils, oil.

NEW JERSEY, ABSIGNOR T0 CHADELOID YORK, N. .A CORPORATION 0F WESTVIBG'IN'IA.V

comme 1929. serial No. 345,205.

patent an important best wrinkling tendencies under differentconditions.

One of the objects of the present invention wrinkle finishes withunspecifically China-wood A further object of this invention is theproduction of such wrinkle finishes with unblown drying oils such asChina-wood oil as ornamental finishes on articles of manufacure.

O ther and further objects and advantages will appear from the moredetailed description set forth below, it bein understood however thatthis more detai ed description is given by way of illustration only, andnot by Way of limitation, since various4 changes may be made therein bythose skilled in the art without departing from the 'scope and spirit ofthe present invention. Y

I n connection with that more detailed descrlption there isshown in theaccompanyingdrawing, in

Figure 1, a plan view of apanel carrying the wrinkle Yfinishof thepresent invention; and in Figure 2, a cross section of such panelenlarged in size to show more clearly the wrinklesiof rugosities of thesurface. For producing the desired effect, compositions are chosen whichunder proper conditions for drying or baking the finish coated article,develop the particular effect herein denominated wrinkle finish. Asstated, an important component of such compositions, is a dr ing oil. Aninvestigation of the various drying oils thatare available shows thatthe conditions under which these drying oils give the best resultsvaries with the particular drying oil being utilized. The more common yused drying oils are linseed oil, perilla oil, and China-wood oil. Theless common drylng oils include chia, citicica,

Walnut, poppy-seed, sunflower, candle nut, lumbang, hempseed, fish, etc.The oils which may be used in the production of wrinkle finishes may begenerically referred to as wrinkling oils.

The production of Wrinkle finishes with drying oils may be separatedinto two groups, first the use of oxidized or preoxidized or blown oils,and second the use of unblown or untreated oils. In general it may besaid that the use of blown or otherwise oxidized oils give highlysatisfactory results. IVith the untreated or unoxidized or unblown oils,China-wood oil stands out as more or less unique. Unblown perilla oiland linseed oil are, relatively weak in their wrinkling power whileunblown or unoxidized China-wood oil exhibits a stronger wrinlding powerthan even the blown forms of linseed oil and perilla oil. China-wood oilmay be said to be the best of the unblown oils for the production ofwrinkling finishes. Experimental comparisons of the relative activity ofthe wrinkling oils in wrinkling finishes may be expressed in a series asfollows: blown Chinawood oil 5; raw China-wood oil 61/2 blown perillaoil S; and blown linseed oil l2. This series expresses the fact that theoil bearing the lowest number is the most powerful, and the order of theoils in their wrinkling acti\' ity decreases as the series rises.

Further comparison of the several oils in relation to the resin contentof the composi tion when such resin is of the wrinkling tinish type tobe further defined below, shows that for the production of the bestresults with such oil-resin compositions, there is a difference in theoil-resin ratios. The more active oils may be used in a smaller ratio ascompared with the resin content, than can be less active oils.

As illustrative of the conclusions set forth in the preceding paragraphthe following may be noted. With blown China-wood oil the bestappearance of the finish is obtained when the ratio of oil to resin isapproximately from 6 to 18 gallons of oil to 100 lbs. of resin. Foruntreated China-Wood oil the ratio is approximately from 8 to 25 gallonsof oil to 100 lbs. of resin. For blown perilla oil the best ratios arefrom 10 to 3() gallons of oil to 100 lbs. of resin while for linseed oil(blown) the best results are obtained with ratios from 14 to 35 gallonsof oil to 100 lbs. of resin. Here again, the difference between the oilsis illustrated, and it is a remarkable and noteworthy fact thatChina-wood oil lies in activity between the most active oil name lyblown China-wood oil, and the other blown oils linseed and perilla. Thisfact also differentiates the unique character of raw Chinawood oil inthese finishes.

There is another feature that serves to distinguish raw China-wood oilfrom the blown or oxidized oils. AOther factors being the same exceptfor variation in the oil utilized, it has been found that when thedrying or baking properties of the compositions containing the severaloils are compared, raw or untreated China-wood oil requiresapproximately ten percent longer drying or heating at a giventemperature for the production of a comparable effect as compared withblo wn lChina-wood oil while blown perilla oil and blown linseed oilrequire from twenty to twenty-five percent longer time treatment thandoes blown China-wood oil.

Without more, therefore, the above considerations are believed to showincontrovertibly that in the production of wrinkle finishes raw oruntreated China-wood oil occupies a unique position.

IVhile specific drying oils are mentioned above, it is understood thatmixtures of the various drying oils having \\'rinkling properties may beused in the production of satisfactory wrinkle finishes, the range ofpropon tions when mixtures are used being the arithmetical mean of theranges of the oils when used without admixture of other wrinkling oils.And while a varnish or other composition to be used to produce a wrinklefinish must contain a substantial proportion of a wrinkling oil,adniixtures ol` the non-wrinkling oils may be used so long as the amountof the latter is not suflieient to eliminate the desired wrinkle effectin the finish obtained. In general it may be stated that in suchadmixtures, for the best effects, not less than half of the oil mixtureshould be a wrinkling oil. For example, two or more wrinkling oils andtwo or more non wrinkling oils may be mixed and a varnish producedtherefrom with the addition of the resin, drier and thinner. In suchcase the sum of the amounts of all of the wrinkling oils present shouldbe desirably at least onehalf of the total oil in the composition. Amongthe non-wrinkling oils there may be mentioned specifically soya beanoil, and other semi-drying or non-drying oils such as cotton-seed, corn,castor, rape-seed. rubberseed, olein, etc. Such non-wrinkling oils maybe either the raw oils, the blown oils, the boiled oils, or otherwisetreated oils.

Of the resins usable in the production of wrinkle finishes which resinsmay be generically referred to as wrinkling finish resins, the followingmay be noted Congo, kauri, damar, Cumar, pontianak, manila, Zanzibar,elemi, mastic, phenol-formaldehyde resins particularly those of theoilsoluble variety. glycerol-phthalic condensation products andparticularly the oil soluble varieties, paracoumarone, Congo ester,rosin ester, and mixtures of these resins and their esters.

Certain substances exhibit a tendency to inhibit the wrinkling effect.Among such -substances there may be noted pyroxylin,

nitrocellulose, gilsonite, and resin. These wrinkle inhibitingsubstances should therefore not be used in any proportion in thecomposition which would prevent the desired development of wrinkles inthe finish; although the may bepresent in lesser proportions an toobtain particular effects. Such wrinkle vinhibiting substances when usedin small amounts have a tendency to produce very fine wrinkles while inlarge amounts they may completely eliminate the wrinkling effect. Rosin'if Aused in large amount, also tends to produce irregularities in thesize and in the interval between wrinkles in the resulting finish. Theapplication'of these wrinkle inhibiting substances to limited areas ofthe surface on -which the wrinkle iinishesare to be developed, is anexpedient that may be used to modify the wrinkle effect at thoseparticular areas. Rosin for example may be used in this inanner.

Solvents or thinners are not a main factor since any moderately volatilesolvent can be of two or more thinning components. The

low boiling thinner evaporates more quickly from the varnish or enamelfilm, romotes the rapid formation of a surface s n, and

during drying `assists in maintaining a greater difi'erentialbetween thedegree of oxidation of the surface skin and the oil within the film.When the finish is dried at elevated temperatures, the use-of ylowboiling thinners also assists in eliminating any tendency toward saggingof the finish during the drying, operation. The following areillustrative of the thinners and solvents that may be used: lightnaphtha, toluol, benzol, petroleum ether or ligroin (benzine), acetone,carbon tetrachloride, alcohol, chloroform, ethyl acetate, etc., andmixtures of these materials. To Some extent, the character of the finishmay be varied by the quantity and character of the thinner used. Moreproynounced wrinkles are produced with compositions containing the lowerboiling thinners, but high boiling thinners such as turpentine may alsobe used. While in the examples given below for illustrative purposes,the use of thelow boiling thinners 1s set forth, this; is4 not to betaken as a limitation for the reasons .set forth above.

Driers and drier combinations are also an important element in thecomposition since the wrinkled eie'ctappears to be somewhat determinedby the rate Tof oxidation of the wrinkling oil. j Suc-'h dris ascobaltacetate, red lead, manganese .f'brate, vlead linoleate, etc., used aloneor'ih" admixture with each other or with other driers `and u'iaterialsare illustrative. Y

A number of examples of'compositions that may be used in production ofwrinkle finishes in accordance with the present disclosure are .setforth below.

Example 1 100 lbs. Congo 4 lbs. rosin 31/2 lbs. red lead 2 lbs.manganese oxide' 10 gals. wood oil l0 gals. light naphtha 32 gals.toluol fIhis example illustrates a 10 gal. varnish using unblownChina-wood oil, and the wrinkling effect obtained is very good.

Example Z 100 lbs. Congo' 4 lbs. red lead 2 lbs. manganese berate 71/2gals. China-wood oil 5 gals. blown linseed oil 5 gals. light naphtha 20gals. toluol Example 3 100 lbs. Congo 4 lbs. red lead 2 lbs. manganeseb'orate 7% gals. China-wood oil 5 gals. boiled'linseedoil 5 gals. lightnaphtha 20 gals. toluol Example 3 illustrates the use of boiled linseedoilin lieu vof the blown' linseed oil of Example 2 the wood oil beingunblown. A

good wrinkling effect is obtained although the wrinkles are somewhatcoarserthan with the composition of Example 2 due to the more pronouncedwrinkling character of blown linseed oil as compared with boiled linseedThis mixture of unblown China-wood oil land blown perilla oil makes a'good wrinkling varnish. Boiled perilla oil may be substituted for theblown perillaoil to yieldrequire but 10% longer treatment than blown.

a satisfactory wrinkling combination, although slightly coarser wrinklesresult.

E'ample 5 lbs. Congo lbs. rosin lbs. red lead lb. manganese borate gals.China-wood oil gals. blown wood oil gals. blown soya bean oil 5 gals.light naphtha 17 gals. toluol This varnish contains blown semi-dryingoil which is of the non-wrinkling type. The effect obtained upon bakingis fairly coarse. The baked film is quite elastic. The soya bean oil ofthis composition may be substituted by othersemior non-drying oils. Forexample raw soya bean oil gives asimilar effect and a flexible film.

In producing the improved wrinkled finish of this invention, it isadvantageous to dry or bake the applied finish of varnish` or enamel,preferably at an elevated temperature depending on the type of articlebeing treated. For lnetal and related surfaces the temperatures mayrange from 150 F. to 450 F., while for wood and related materials, thetemperature range may be from 120 F. to 140 F. These temperatures aremerely illustrative. At elevated temperatures ra id oxidation of thesurface of the applied lm is promoted and any tendency toward diffusionof oxidation products from the surface into the interior of the film islessened. In general, drying at elevated temperatures accentuates thewrinkling and assists in providing a harder finish. As an illustrationof the relation between the drying periods and temperatures of drying orbaking to produce satisfactory wrinkle finishes the following are'given.With compositions that give satisfactory effects by five hour treatmentat 180 F. similar treatment for three hours at 200 F., or two hours at250* F., or one and one-half hours at 300 F., and approximatelythree-fourths of an hour at 400 F., may be used. As stated above, thewrinkling finish composition containing wrinkling oils of theperilla-linseed type require from 20 to 25% longer heat treatment at thesame temperature as do similar compositions utilizing blown wood oil,while the compositions utilizing unblown wood oil 4 la a 21.1. 61/2 woodoil.

Increase in the amount of oil in the compositions results in Wrinklingat lower temperatures and hence when lower temperatures are to be usedin connection with for example, wood and related articles, thecompositions may desirably contain more oil. Further as -illustrated byExample 5 above, the higher oil content gives increasedelasticity andflexibility so that long oil compositions are particularly desirable foruse on metal stamping, or on leather, paper, cloth, rubber, etc.

There have been given above a number of considerations directed to typesof composition and baking temperatures which affect the character of thewrinkles produced in the finish. Other factors however may also beutilized to modify the type of' wrinkled effect obtained. For examplethe thickness of the applied film will result in differences in thewrinkle effect. v Thinner films give finer wrinkles, while thicker filmsyield coarser wrinkles. When spraying is used to apply the composition,spray nozzles giving coarse atomization give greater deposition ofcomposition and consequently coarser wrinkles, while on the other hand,spray nozzles of finer atomization give thinner films with finerwrinkles.

For the production of wrinkle finishes having a textured effect by theproduction of aC- centuated rugosites at certain points or areas in thefinish, the article to be treated may desirably be coated with arelatively heavy coating of the desired com iosit-ion and baked in aninclined position wl ich inclined position may vary from a small angleto the horizontal to a vertical position.

The incline of the surface of the article bearing the coating produces aflowing or movement of the wrinkle finish coating after it is appliedand at or about the time when the baking commences and before the bakinghas caused the setting of the finish to take place to an extent wheresuch movement or flowing would be precluded. The effect of suchtreatment is to roduce waves or areas of accentuated rugoslties orwrinkles in the more uniformly developed wrinkled finish. Curtain andsag effects are thus produced, and China-wood oil compositions areparticularly adapted to the production of the so-called pine-treeeffects in which the accentuated rugosities at a particular point appearto radiate more or less from a limited area and to spread outwardly anddownwardly from the pointI where the accentuated rugosity first appearsin the finish during the baking operat-ion. The flowing or movement ofthe wrinkled coating after it is applied which results in theaccentuated effects noted above, may be accomplished in other ways thanmerel by gravity due to the position of the work. For example aircurrents or other flowing methods may be used.

When gang sprays are used to apply the composition, at certain pointsthe atomization may be made coarser to produce heavier or thicker layersat these points resulting in coarser wrinkles in such thicker layers.Accentuated rugosities distributed in the more. uniformly wrmkledfinishes may be produced in this manner.

The wrinkle finishes are characterized by hiding quality is used in moreor less the` same meaning that the expression covering power is used inthe paint art. It is a remarkable thing for example that a single coatof unpigmented Wrinkle finish may be applied to a brightmetal surfaceandthe resulting finish will completely mask the metal surface. Priorart paint compositions on the other hand invariably require at leastseveral coats in order to secure a comparable vhiding effect. Theapplication for example of a single coat of Wrinkle finish to a brightmetal surface which is silvery in color or appearance, results in abrass or bronze appearing Wrinkle finish. The exact brass-or bronzeeffect can be varied by increase or decrease in the temperature at whichthe baking is effected.

The drawing illustrates the. more or less uniformly distributed Wrinklefinish that may be obtained with the present invention.

yThe coating B carried by .the panelA, pre'- sents a rugose'or wrinkledsurface, in Which the Adistribution of wrinkles is not regular, but theWrinkles are more or less uniformly distributed over the entire surface.

The baked or dried finishes of the present invention are particularlyresistant to softening by lacquer compositions or the solvents used insuch compositions, so that although the rugose surfaceaffords a veryextensive area for the action of Such solvents or lacquers e.nitrocellulose lacquers), the baking creates a resistance to suchsoftening action.

Consequently, the wrinkle finishes and compositions used for producingsuch coatings are particularly desirable as undercoats Where a Wrinkleeffect is desired, and such coats may then be'giveii one or more coatsof pyroxylin enamels, oil enamels, or baking When wrinkle finish whichhave a tendency to change or to darken under the action of elevatedtemperatures, these finishes may be coated with pyroxylin lacquercompositions.

While certain theoretical consider-ations have been set forth above inan attempt to explain ,some of the effects obtained, it should beunderstood that this invention is not limited by such theoreticalconsiderations because the compositions and methods discussedaboveenable the results herein disclosed to a be obtained, and the exactinterpretation of the reasons for these results is of little moy ment.It is sufficient that the extremely 'novel and highly ornamental effectsmay be pigments are used in thev resin, drier and thinner in proportionsto yield a Wrinkle finish when dried. A

2. A Wrinkle finish composition as set forth in claim 1 containing anadditional Wrinkling oil as well as untreated Chinawood oil. v

3. A Wrinkle finish composition as sel'. forth in claim 1 containing anon-Wi'inkling oil in an amount insuiiicient to prevent the desiredWrinkle finish.

4.. A composition as set forth in claim l in Which the ratio of oil to'resin is from 8 to 25 gallons of oil to 100 lbs. of resin.

5. An article of manufacture carrying a coating resulting from thecomposition of claim 1. 6. An article of manufacture carrying a coating'resulting from thc composition of claiin 1 in Which the ratio of oil toresin is from 8 to 25 gallons of oil to 100vpounds of resin andcontaining oil in an amount suflicient to give the coating substantialfiexibility. A

7. An article of manufacture carrying a baked coating resulting' fromthe composition of claim 1.

8. An article of manufacture carrying a ybaked coating resulting fromthe composition of claim 1, the coating exhibiting areas of accentuatedrugosities.

9. An article of manufacture carrying a relatively thin coatingresulting from the composition of claim 1, said coating exhibiting fineWrinkles.

- 10. An article of manufacture carrying a relatively heavy coatingresulting from the composition of claim 1, said coating exhibit- Y quercomposition.y

13. T-he process of producing vvrinkling finishes on articles lofmanufacture Which-y comprises applying thereto a Wrinkling finishcomposition as set forth in claim 1, and drying the coating at atemperature Which produces a Wrinklev finish.

14. The process of producing wrinkling finishes on articles ofmanufacture which comprises applying thereto a Wrinkling finishcomposition as set forth in claimV 1, in which the ratio of oil to resinis from 8 to 25 gallons of oil to 100 pounds of resin and drying thecoating at a temperature of from F'. to 450 F'.

15. The process of producing wrinkling finishes on articles ofmanufacture which comprises applying thereto a wrinkling finishcompos1tion as set forth in claim 1, and baking the coating underconditions to produce a wrinkle iimsh carrying accentuated ru osities.

16. T e process of producing finishes on articles of manufacture whichcomprises applying thereto the composition of claim 1, in which theratio of oil to resin is from 8 to 25 gallons of oil to 100 ounds ofresin baking the coating, and app ying thereover, a nitrocelluloselacquer composition.

17. An article of manufacture carrying a coating comprising an undercoatof a raw China-wood oil wrinkle lfinish composition, and a protectingovercoat on the wrinkled undercoat.

18. A Wrinkle finish composition comprising raw China-wood oil and anon-wrinkllng oil, the proportion of the latter being insuficient toprevent substantial wrinkling of the composition when dried on a surfacecoated therewith.

19. An article of manufacture carrying a wrinkled coating of arawChina-woodl oil wrinkle finish composition.

20. An article of manufacture carrying a wrinkled coating of a rawAChina-wood oil wrinkle finish composition containing a nonwrinkling oilin an amount insufficient to prevent substantial wrinkling of thecoating composition, but sufficient to yield increased flexibility tothe coating.

21. An article of manufacture carrying a raw China-wood oil wrinklefinish composition including a non-wrinkling oil, the latter beingpresent in an amount insufficient to prevent substantial wrinkling inthe coating, and a protecting overcoat on the wrinkled coating.

22. An improved'varnish orl enamel composition for producing wrinklednishes comprising China-wood oil and a resin, a drier and a thinner inproportions to yield a wrinkled finish upon dr ing.

23. The process of pro ucing coatingson articles of manufacture whichcomprises applying'to the surface of such article a dryin oil comosition adapted upon baking to iel a wrin led finish coatin, andthen ba'ng the coated article to produce a' wrinkled finish coating.

24. The process of producing coatings on articles of manufacture whichcomprises apto yield a wrinkled finish coating, and then baking thecoated article to produce a wrinkled finish coating.

26. The process of producing coatings on articles of manufacture whichcomprises applying to the surface of such articles a compositioncontaining oxidized China-wood oil adapted upon baking to yield awrinkled finish coating, and then baking the coated article to produce awrinkled finish coating.

27 The process of producing coatings on articles of manufacture whichcomprises applying to the surface of such articles a thick film of adrying oil composition adapted upon baking to yield a coarsely wrinkledfinish coating, and then baking the coated article to produce a coarselywrinkled finish coating.

28. The process of producing coatings on articles of manufacture whichcomprises applying to the surface lof such articles a thin film of adrying oil composition adapted upon baking to yield a finely wrinkledfinish coating, and then bakin the coated article to produce a finelywrin led finish coating.

FRANK BRIAN ROOT.

plying to the Isurface of such articles a blown drying oil compositionadapted upon baking to yield a wrinkled finish coating, and then bakinthe coated article to produce a wrin- Y kled nish coating.

25. The process of producing coatings on articles of manufacture whichcomprises apl plying to the surface of such articles a Chinawood oilcomposition adapted upon baking

